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Experiment 1: Determination of Some Structural Features of Metal Complexes by

Infra-Red Spectroscopy
Ong Zhy Hui
21572185 7th Feb 2017

Title: Experiment 1 Determination of Some Structural Features of Metal Complexes


by Infra-Red
Spectroscopy

Aims:
Part A: To prepare cis- and trans- isomers of big glycinato Cu(II) and to identify
the stereochemistry of
the complexes by using infra-red spectroscopy and the principles of group
theory.
Part B: To prepare a Cu(II) complex of dimethyl sulfoxide (DMSO) and to
determine the coordination
mode (O- or S-bound) for DMSO complexes of three different metal ions:
Cu(II), Ru(II) and Pd(II).
To compare experimental results with assignments predicted by the principle
of Hard and Soft
Acids and Bases.

Abstract:
Part A: The Isomers for Cu(gly-)2.H2O are both synthesized. The weight and the
percentage of yield of the
products are recorded and calculated. The IR Spectra for Isomer 1 and Isomer
2 (with 2 methods)
are also studied. The functional groups are identified with the IR Spectra and
the Frequency
Range for different bond type.

Part B: CuCl2.2DMSO was synthesised and studied. Dimethylsulfoxide (DMSO) is


an ambidentate ligand,
which it has two different sites in which an atom can bind to. These two sites
are either sulphur
or oxygen on DMSO. Using infrared spectroscopy, the site in which Pd, Ru and
Cu bind to on
DMSO can be determined by the absorption of the S=O bond, which absorbs
at around 1050cm-1. So the IR spectrum of the, PdCl2.2DMSO, RuCl2.4DMSO
and CuCl2.2DMSO were measured.

Methods:
Part A: Preparation and Characterisation of the Geometric Isomers of a
Coordination Complex: Cis- and
Trans- Bis Glycinato Copper (II) Monohydrates

Preparation of Cu(gly-)2.H2O Isomer 1 - Copper (II) acetate monohydrate (2.0 g)


is dissolved in
hot deionized water (25 ml) in a 100 ml Erlenmeyer flask. Hot ethanol (25 ml)
is added to the
solution and the temperature is maintained at about 70C. Glycine (1.5 g) is
dissolved in hot
deionized water (25 ml) in a separate Erlenmeyer flask. The two solutions are
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Experiment 1: Determination of Some Structural Features of Metal Complexes by
Infra-Red Spectroscopy
Ong Zhy Hui
21572185 7th Feb 2017

mixed while hot


and gently swirl the flask. The resulting mixture is cooled to room
temperature. The precipitation
of the product is completed by transferring the flask into an ice-water bath for
about 10 minutes.
The product is collected by suction filtration using a Buchner funnel. The
filtrate is preserved in a
separate flask before washing the product with ethanol.

Preparation of Cu(gly-)2.H2O Isomer 2 (Method 1) Cu(gly-)2.H2O (isomer 1),


(1.5 g), extra glycine
(1.0 g) and the filtrate preserved from the above reaction (10 ml) are placed
into a 100 ml round
bottom flask. The mixture is carefully heated on an oil bath at reflux for 1
hour. The solid is
collected by suction filtration using a Buchner funnel and air dried. (Method 2)
-
Cu(gly )2.H2O
(isomer 1), (0.2 g) is placed in an evaporating dish and heated in an oven at
about 180C. The
reaction shown below is completed in 30 minutes. The solid is removed from
the oven and
cooled to room temperature.

[Cu(gly-)2.H2O (isomer 1)] (s) [Cu(gly-)2 (isomer 2)] (s) + H2O (g)

Part B: Metal Complexes of Dimethyl Sulfoxide (DMSO)

Preparation of CuCl2.2DMSO Copper (II) chloride (670 mg, 5 mmol) is


dissolved in ethanol (5 ml)
in a 10 ml Erlenmeyer flask equipped with a stirrer bar. DMSO (1 ml) is slowly
added to the
stirred solution. A light green product is yielded by the immediate exothermic
reaction. The
mixture is stirred for a few minutes. The product is collected by a vacuum
filtration using a Hirsch
funnel. The product is washed with two 2 ml portions of cold ethanol, followed
by equal portions
of diethyl ether. The product is dried in a vacuum desiccator.

Results:
Part A: Preparation of Cu(gly-)2.H2O Isomer 1

Formula weight of Cu(II)(OAc)2.H2O = 199.65 g mol-1


Weight of Cu(II)(OAc)2.H2O = 2.000 g
Moles of Cu(II)(OAc)2.H2O = 0.01000 mols

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Experiment 1: Determination of Some Structural Features of Metal Complexes by
Infra-Red Spectroscopy
Ong Zhy Hui
21572185 7th Feb 2017

Formula weight of product Cu(gly-)2.H2O = 229.68 g mol-1


Weight of product = 2.113 g
Moles of product = 0.00920 mols

Equation for reaction: (CH3CO2)2Cu.H2O + 2NH2CH2CO2H


Cu(NH2CH2COO)2.H2O + 2CH3COOH

0.00920
% yield of Cu(gly-)2.H2O Isomer 1 =
100
0.01000

= 92.00%

Preparation of Cu(gly-)2.H2O Isomer 2

Formula weight of product Cu(gly-)2.H2O (Isomer 1) = 229.68 g mol-


1

Weight of Isomer 1 used = 1.500 g


Moles of Isomer 1 used = 0.00653 mols

Formula weight of product Cu(gly-)2.H2O (Isomer 2 Method a) = 229.68


-1
g mol
Weight of product (Isomer 2 Method a) = 1.226 g
Moles of product (Isomer 2 Method a) =
0.00534 mols

% yield of Cu(gly-)2.H2O Isomer 2 Method a =


0.00534
100
0.00653

= 81.78%

Formula weight of product Cu(gly-)2.H2O (Isomer 2 Method b) = 229.68


-1
g mol
Weight of product (Isomer 2 Method b) = 0.231 g
Moles of product (Isomer 2 Method b) =
0.00101 mols

% yield of Cu(gly-)2.H2O Isomer 2 Method b =


0.00101
100
0.00653

= 15.47%

Part B: Preparation of CuCl2.2DMSO

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Experiment 1: Determination of Some Structural Features of Metal Complexes by
Infra-Red Spectroscopy
Ong Zhy Hui
21572185 7th Feb 2017

Formula weight of copper (II) chloride = 170.48 g mol-1


Weight of copper (II) chloride = 0.860 g
Moles of copper (II) chloride = 0.00504 mols

Formula weight of product CuCl2.2DMSO= 290.72 g mol-1


Weight of product = 1.242 g
Moles of product = 0.00427 mols

Equation for reaction: CuCl2 + 2DMSO CuCl2.2DMSO

0.00427
% yield of CuCl2.2DMSO =
100
0.00504

= 84.72%

Table 1: IR peaks of PdCl2.2DMSO, RuCl2.4DMSO & CuCl2.2DMSO from


IR Spectra

DMSO Coordinated by Sulphur


IR Peaks
Complexes or Oxygen
PdCl2.2DMSO 1089.9 cm-1 Sulphur
1096.3 cm-1 & 922.4 Sulphur & Oxygen
RuCl2.4DMSO
cm-1
CuCl2.2DMSO 915.9 cm-1 Oxygen

Discussion:

Part A: (i) Table 2: Functional group frequencies for the glycine ligands of the two
complexes.

Type of
Frequency (cm-1) Bond Type Functional Group
Complexes
Hydrogen Bonded
3330.87 3157.09 O-H
Alcohols
1573.53 C-C Aromatic C-C bond
1385.14 C-H Alkanes
Isomer 1
1319.76 C-N Amines
Alcohols, Ethers,
1117.50 C-O Esters, Carboxylic
Acids
Hydrogen Bonded
3309.08 3261.58 O-H
Alcohols
1605.01 1583.74 C-C Aromatic C-C bond
1383.12 C-H Alkanes
Isomer 2
1328.49 C-N Amines
Alcohols, Ethers,
1149.88 C-O Esters, Carboxylic
Acids

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Experiment 1: Determination of Some Structural Features of Metal Complexes by
Infra-Red Spectroscopy
Ong Zhy Hui
21572185 7th Feb 2017

(ii) Isomer 1 shows 2 number of Cu-O Infra-red stretches and 2 number of Cu-
N Infra-red
Stretches. Whereas Isomer 2 shows only 1 each for the number of Cu-O
and Cu-N Infra-red
stretches. This showed that the stereochemistry of Isomer 1 is in cis- form
and Isomer 2 is in
trans- form.

Part B: 1. Yes. The experiment results conform to the principle of Hard and Soft
Acids and Bases (HSAB).
As DMSO can act as a hard and soft base, then metals could be able to
bind to a DMSO as soft
and hard acid. For a metal that bind to Sulphur atoms, then the metal is a
soft acid. This is
because metal is donating electrons to the Sulphur atoms which increases
the absorption
frequency. For a metal that binds to oxygen atom, then the metal should be
a hard acid as the
metal will form a bond with a lone pair from the oxygen. The result of
bonding with a long pair
will decrease the absorption frequency. Based on the IR result, PdCl 2 binds
to Sulphur which
indicated that it is a soft acid. RuCl 2 binds to both Sulphur and Oxygen
sites, it can be soft acid
and hard acid. CuCl2 binds to the oxygen indicates that it is a hard acid.

2. Au+ is a soft acid, it will form stable complexes when it binds to PPh 3 (soft
base).
Fe0 is a soft acid, it will form stable complexes when it binds to CO & PPh 3
(soft bases).
Cr3+ is a hard acid, it will form stable complexes when it binds to C 2O42- &
H2O (hard bases).
Rh+ is a soft acid, it will form stable complexes when it binds to CO & PPh 3
(soft bases).

3. I predict that the DMSO is coordinated to Ni(II) by the O- atom, which


indicates that it is a hard
acid. Therefore, this result is consistent with that expected based on the
principle of Hard and
Soft Acids and Bases (HSAB).

Conclusions:

Part A: The percentage yield obtained for the product Cu(gly -)2.H2O Isomer 1 is
92.00%. The percentage
yield obtained for the product Cu(gly-)2.H2O Isomer 2 Method a is 81.78%
whereas for Method
2, it is only 15.47%. The functional groups for both Isomer 1 and 2 are
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Experiment 1: Determination of Some Structural Features of Metal Complexes by
Infra-Red Spectroscopy
Ong Zhy Hui
21572185 7th Feb 2017

identified and tabulated in


Table 2. Both isomer 1 & 2 showed that the significant functional group are O-
H bond (Hydrogen
bonded Alcohols), C-C bond (Aromatic C-C bond), C-H bond (Alkanes), C-N
bond (Amines) and C-O
bond (Alcohols, Ethers, Esters, Carboxylic Acids).

Part B: The percent yield obtained for the product CuCl 2.2DMSO is 84.72%.
Metals have been identified
as either soft or hard acid by using the Hard and Soft Acids and Bases (HSAB)
theory and the IR
spectra. For Pd is a soft acid, Ru is both a hard & soft acid as it can bind to
both O- & S- atom of
DMSO whereas Cu is a hard acid.

References:

1. T. Bora and M. M. Singh* Department of Chemistry, Dibrugarh University,


Sulphoxide Complexes of Ruthenium Assam, India (September 24 th, 1977)
2. C. V. SENOFF, E. MASLOWSKY, JR., AND R. G. GOEL Department of Chemistry,
Canadian Journal of Chemistry, University of Guelph, Guelph, Ontario, May 6,
1971

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